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Low-temperature oxidation of CO catalysed by Co3O4 nanorods

Nature volume 458, pages 746–749 (2009)Cite this article

Abstract

Low-temperature oxidation of CO, perhaps the most extensively studied reaction in the history of heterogeneous catalysis, is becoming increasingly important in the context of cleaning air and lowering automotive emissions1,2. Hopcalite catalysts (mixtures of manganese and copper oxides) were originally developed for purifying air in submarines, but they are not especially active at ambient temperatures and are also deactivated by the presence of moisture3,4. Noble metal catalysts, on the other hand, are water tolerant but usually require temperatures above 100 °C for efficient operation5,6. Gold exhibits high activity at low temperatures and superior stability under moisture, but only when deposited in nanoparticulate form on base transition-metal oxides7,8,9. The development of active and stable catalysts without noble metals for low-temperature CO oxidation under an ambient atmosphere remains a significant challenge. Here we report that tricobalt tetraoxide nanorods not only catalyse CO oxidation at temperatures as low as –77 °C but also remain stable in a moist stream of normal feed gas. High-resolution transmission electron microscopy demonstrates that the Co3O4 nanorods predominantly expose their {110} planes, favouring the presence of active Co3+ species at the surface. Kinetic analyses reveal that the turnover frequency associated with individual Co3+ sites on the nanorods is similar to that of the conventional nanoparticles of this material, indicating that the significantly higher reaction rate that we have obtained with a nanorod morphology is probably due to the surface richness of active Co3+ sites. These results show the importance of morphology control in the preparation of base transition-metal oxides as highly efficient oxidation catalysts.

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Figure 1: TEM images of Co 3 O 4 nanorods.
Figure 2: Effects of moisture content, regeneration and temperature on the oxidation of CO over Co 3 O 4 nanorods.
Figure 3: Possible reaction pathway for CO oxidation on Co 3 O 4 nanorod.
Figure 4: Reaction kinetics of CO oxidation.

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Acknowledgements

We thank C. Li, L. Lin and X. Bao of the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, for their encouragement and discussions. We also acknowledge financial supports for this research work from the National Natural Science Foundation of China and the National Basic Research Program of China.

Author Contributions X.X. and Y.L. performed the synthesis of Co3O4 nanorods/nanoparticles and the catalytic tests. Z.-Q.L. conducted the transmission electron microscopy observations and structural analysis. M.H. and W.S. designed the study, analysed the data and wrote the paper. All authors discussed the results and commented on the manuscript.

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  1. Xiaowei Xie and Yong Li: These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

    Xiaowei Xie, Yong Li & Wenjie Shen

  2. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

    Zhi-Quan Liu

  3. Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji 192-0397, Tokyo, Japan,

    Masatake Haruta

  4. Japan Science and Technology Agency, CREST, 4-1-8 Hon-Cho, Kawaguchi 332-0012, Saitama, Japan ,

    Masatake Haruta

Authors
  1. Xiaowei Xie
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Correspondence to Wenjie Shen.

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Xie, X., Li, Y., Liu, ZQ. et al. Low-temperature oxidation of CO catalysed by Co3O4 nanorods. Nature 458, 746–749 (2009). https://doi.org/10.1038/nature07877

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